US 2195088 A
Description (OCR text may contain errors)
Mata Mar. 26, 1940 PATENT OFFICl-l' 1 2,195,083 'SULPHONATED KETONES Helmnt Kcppler,
Leverknsen-Wiesdorfl and Rudolf Schroetcr, Iieverknpen-Schlebusch, Germany,
assignors. to- I; G. Farbenindustrle 'Akticnge'sellschaft, Frankfort on the 7 Main,
-'Germany No Drawing. Application April 18, 1939, Serial No. 268,522. In Germany April 30, 1938 4 Claims. (c1. 200-503) The present invention relates to sulphonated ketones.
It is known to produce ,water-soluble products from symmetric higher aliphatic ketones which are obtainable by distillingthe calcium salts of proposed to use such sulphonation products in 15 the treatment of textiles, for instance, as soften-' ing, wetting and cleansing agents. Sulphonation of such symmetric ketones does not take place very easily. Higher temperatures, large quantities of a strong sulphonating-agent lo and, if catalysts are used, large amounts of the same are necessary in order to obtain clearly water-soluble products. It has been established that under such conditions a relatively large amount of the ketone' is several times sulphov, nated; the properties of such polysulphonated products, however, are not so good in some respect when compared with mono-sulphonated compounds. On the other hand, if sulphonation is carried out under milder conditions, the prod- [ucts will not become completely water-soluble,
since part of the starting material remains unsulphonated. Isolation of the mono-sulphonated products from this mixture is too complicated and expensive as to come into question.
"'0 We have now found that new products of improved properties can be obtained on 'a similar basis by sulphonating ketones of the general formula R-COR;1, in which R is an aliphatic, cycloaliphatic 'or hydrogenated aromatic-an w. phatic hydrocarbon radical having at least 6 'carbon atoms directly connected with each other, and R1 is a saturated aliphatic'hydrocarbon radical having at the most 4 carbon atoms directly connected to each other. The hydrocarbon radicals may be straight or branched. Sulphonation of such ketones proceeds very uniformly under relatively mild conditions so that perfectly water-soluble products which mainly consist of the corresponding monosulphonic;
5o acids can be obtained therefrom in a very good yield. The properties of these products are, therefore, superior inmany respects to those of the above mentioned known sulphonation products of higher symmetric aliphatic ketones,
3 It may be mentioned at this point that it is also-known to halogenate ketones of the general formula R'COR'1, in which R. is an aliphatic hydrocarbon radical of more than 8 carbon atoms and R1 is an' aliphatic hydrocarbon radical of less than 5 carbon atoms, and to exchange the halogen atom for the sulpho group by reaction with alkali sulphite. The products obtained thereby were to be used as wetting, dispersing and cleansing agents. Their properties, however, are inferior to those of our new products which are obtained by direct sulphonation; moreover, the above process is complicated and thereby more expensive than the present simple and cheap sulphonation method.-
As starting material forthe'present production of our new products there may be mentioned ketones-of the above general formula in which R is a'hydrocarbon radical corresponding to the radicals ofone of the following acids: lauric acid, palmitic acid, stearic acid, mixtures of saturated fatty acids as are obtained from natural fats, oils or by oxidation of paramnsif necessary, after hydrogenation-of naphthenicacids, resin acids, hexahydrobenzoic acid, hydroabietic acld, and'R1 is the methyl, ethyl, propyl or butyl radical. Moreover, there may be further mentioned ketones which are obtainable by condensation of suitable aldehydes with suitable ketones and reducing the double bond of the condensation product.
Sulphonation is carried out according to known methods by treating the said ketones with concentrated sulphuric acid, monohydrate, oleum,
chlorosulphonic acid etc., if desired at elevated temperature.
small quantities of unsulphonated starting ma-- terial the reaction products can be easily freed by heating under reduced pressure, or by. extracting their aqueous solutions or the solid products, for instance, with benzine, gasoline etc.
It has been found to be especially advantageous to sulphonate the products dissolved in a socalled active solvent, 1. e. derivatives of low molecular aliphatic carboxylic acids, especially anhydrides, halides and nitrlles, or ethers, like for instance dimethyl-, diethyl-, dibut'ylether, dioxane, tetrahydrofurane etc. When using such solvents the reaction can be carried. out with about the calculated amount of sulphonating agent in very short time and with excellent yield. No further purification of the reaction products is necessary in this case.
When solid ketones are to be em-, ployed, sulphonation is preferably carried out in Our. new sulphonation products are very resistant to hard water, to acids and alkalies. Especially whentheir molecular weight is not too high, they are soluble even in liquids containing large amounts of electrolytes, for instance, in mercerizing lyes. The higher molecular sulphonation products give with water strongly foaming solutions having a good wetting, emul-- The.
225 parts of undecylpropyl ketone having-a melting point of 28 C. are dissolved in -to parts of acetic acid anhydride; in the course of one hour 120 parts of chlorosulphonic acid are added to the solutionwhile stirringv and cooling to 25 C. The homogeneous sulphonation mass is left standing at room temperature for about 4 to 6 hours and is thereupon introduced into a mixture of 350 to 400 parts of volume of 34% caustic soda lye and ice, while stirring; the temperature is kept at about 25 to 35 C. The reaction of the aqueous solution is kept alkaline.
After 1 to 2 hours stirring, the solution is warmed to 80 C." It is then left standing for some time, whereupon the salt solution at the bottom is extracted; about 500 parts of a slimy colored mass remain which can be lightened by stirring with some chlorine lye. This mass dissolves easily inwarm water; the solution foams strongly and possesses a very well wetting action.
If, instead of the undecylpropyl ketone, 185
parts of a ketone prepared from coconut fatty acid and acetic acid are used, a clear solution containing about 15% of the reaction product is obtained after neutralization of the sulphonation mass with caustic soda lye of about 10% strength. This product dissolves clearly in .a mercerizing lye of 32 B.-
Example 2 about 2 hours at 30? C.; after stirring is stopped,
soon a pasty brown mass separates which canbe isolated by withdrawing thesalt liquor ,or by filtration through a folded filter. In this manner about 1450 parts of alight brown reaction product are obtained which is clearly soluble in hot water and which can be freed from salt and water by drying and extracting with organic solvents, as for instance alcohol. The product shows a good wetting-, dispersingand equalizing capacity.
Highly valuable products are also obtained by employing acetonitrile or acetyl chloride or ether when sulphonating, instead of acetic acid anhydride.
A product which'is especially suitable as laundry washing agent is obtained by sulphonating heptadecylmethyl ketone in carbon tetrachloride persing capacity.
solution by meansof equal amount of 30% oleum.
Example 3 parts oi a mixture of methyl ketones, obtained from paraflin fatty acids (a mixture of fatty acids obtained by the oxidation of parafline) of the average molecular weight-of 142 and from. acetic acid, are stirred for several hoursat 20 to 30 C. with 270 parts of 30% oleum. The sulphonation mass is thereupon stirred into a mixture of 420 parts by volume of 34% aqueous caustic soda solution and 800 parts of ice. A clear, darkly colored solution obtained which can be clarified by adding some hydrogen perox: v
ide. This solution remains completely clear when stirred into a great excess of aqueous caustic soda solution of 32 B.
The sulphonation of the paraffin methyl ketones may.also be carried out in a carbon tetrachloride, ether, acetic acid, acetic acid ethyl ester etc.
When sulphonating the corresponding butyl paraffin ketones with chlorosulphonic acid in the presence of propionic acid anhydride, the resulting product is distinguished-by a very good wetting capacity in baths which are poor in electrolytes.
250 parts of a ketone-mixture prepared from naphthenic acid and acetic acid are dissolved in 500 parts of diethyl ether and sulphonated by slowly adding 190 parts of chlorosulphonic acid at 20 to 25 C. The sulphonation-mixture is kept standing for some time and is then stirred, while cooling with ice, into excess dilute aqueous caustic soda lye; stirring is continued for some hours. After stirring-is stopped, the liquor containing the sulphonation product can be separated from the ether layer. The liquor is then neutralized and evaporated to dryness. The. reaction product can be. isolated-byextraction with. The substance thus obtained is clearly I alcohol. soluble in water; the solutions show a good dis- Instead of the lowly boiling'in'flammable diethyl ether, the higher boiling dibutyl ether can be employed at the sulfonation; also-dioxane or ethylbutylether may be used as solvent.
- Example 5 parts or methyl ketone obtained by condensing a-ethylhexyl aldehyde with acetone and hydrogenating the double bond, are sulfonated with chlorosulphonic acid in the presence of butyric acid chloride. The sulphonation mass is worked up as described in Example 3. The reaction product dissolves clearly in water, which may contain considerable quantities of salts, and yields foaming solutions therewith.
Example 6 340 parts of an asymmetric ketone obtainedfrom hydroabietic acid and butyric acid are dissolved in ether and treated with-'120 parts of chlorosulphonic acid at 20 to 30 C. The solution is kept standing for some time and is then stirred into an excessdilute caustic soda lye: The ether is evaporated after neutralizing the free alkali and the remaining aqueous solution is evaporated to dryness. Thus a product is obtained which is clearly soluble in water, the solutions of which foam strongly and show a good washing, wetting and dispersing capacity.
If instead of the above-mentioned ketone, a
resinic acid alkylketone is used, the sulphonation 7 product can be used as capillary active substance and also as finishing agent.
1. Process for preparing new sulphonation products which comprises directly sulphonating a ketone of the general formula RCO-R1 in which R is a saturated aliphatic, cycloaliphatic or hydrogenated aromatic-aliphatic hydrocarbon radicle containing at least 6 carbon atoms direct- 1y connected to each other, and R1 is a saturated aliphatic hydrocarbon radicle containing at the most 4 carbon atoms directly connected to each other.
2. Process for preparing new sulphonation products which comprises directly sulphonating a ketone of the general formula RCOR1 in which R is a saturated aliphatic, cycloaliphatic or hydrogenated aromatic-aliphatic hydrocarbon radicle containing at least 6 carbon atoms directly connected to each other, and R1 is a saturated aliphatic hydrocarbon radicle containing at the most 4 carbon atoms directly connected to each other, the ketone being dissolved in an active solvent selected from the group consisting of bon atoms directly connected to each other, and
R1 is a saturated aliphatic hydrocarbon radicle containing at the most 4 carbon atoms directly connected to each other.
4. As new products monosulphonates having been obtained by direct sulphonation of ketones of the general formula-R-CO-R1 in which R is a saturated aliphatic, cycloaliphatic or hydrogenated aromatic-aliphatic hydrocarbon radicle containing at least 6 carbon atoms directly connected to each other, and R1 is a saturated allphatic hydrocarbon radicle containing at the most .4 carbon atomsdirectly connected to each other.
HELMUT KEPPLER. RUDOLF SCHROETER.